DE1522408A1 - Antistatic layer for photographic materials - Google Patents

Description

Antistatic layer for photographic Materials.

BLe present invention relates to photograph! - see films with improved anti-static protective layers.

Due to the accumulation of electrical charges on photographic films arise both in their production and in their use great difficulties. This· Static electrical charges can build up due to the friction dee 711ms on the rollers or other parts of the device through which the film passes, through contact old rough surfaces or caused by a variety of other known reasons. Static discharges,

± = 2-122

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Unfailed in accordance with Art. 7 § 1 Paragraph 2 No. 1 Sentence 3 of the Amendment Act. ν. 4,9.19SZ1 BAD OfW3 »N

Anything that occurs in the film before developing is recognizable after the film has been processed by irregular stripes or lines or dark dots, which can be attributed to the lightning-like exposure of the emulsion in these areas. Static charges produce PlIo _9, especially in the filia intended for cinematography, are also undesirable, since this increases the friction when the film "passes through" the picture windows or other parts of the projection device.

This can cause electrostatic charges to build up on the film surfaces be reduced by adding matting agents to the protective layers, which improve the adhesion between the layers Degrades films. Once a charge has occurred, it can still be made more electrically conductive by adding Remove materials from the protective layer. You can also combine both options.

Fi previous attempts to prevent static electricity in photographic films was mostly a leading one or hygroscopic material is applied to the surface of the film, so as to increase the electrical conductivity of the film su increase. Much of these materials, however, are old than the substances that see one or more layers of the photograph Form films, incompatible and thus lead to new difficulties in production.

Quaternaries as la photographic materials are

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most of them cannot be used because they create veils. Hygroscopic Agents such as glycerine, potassium acetate and LlCl lead to sticking of the layers and are at low levels Humidity ineffective. Higher molecular carbon or Sulfonic acids such as sodium polystyrene sulfonic acid and sodium polyvinyl sulfonic acid, directly to one hydrophobic layer support used, a good antistatic effect, but this when used in gelatine or emulsion layers falls sharply. Chromium complexes react with the gelatine and can therefore only be used under certain conditions.

Many compounds that have a good antistatic effect change the castability when added to gelatin solutions of the casting solutions, especially when using Kell and vacuum alrbrush casters. Irregular ones arise Layer surfaces.

The invention is based on the object of finding antistatic agents which are photographically inactive and which can be used as an additive for photographic protective gelatin layers.

It has now been found that layers with very good antistatic effectiveness are obtained if the water-permeable layer is used Layered colloid e.g. a protein, preferably gelatin, Photographically inactive urethanes or esters of alkoxylated or alkoxylated fatty alcohols, which are sparingly soluble in water, are photographically inactive Adds alkylphenols or the substances mentioned

179 _ 3. 909833/1142

ORIGINAL

■ s according to known methods on flame material with a black hat without antistatic agents. The compounds have the following, general formula:

- (CH ₂ -CH-O) _- - (CH ₂ -CH ₂ -O) - CO 17 _y R ¹ CH ₃

in which mean

a · alkyl with 6-18 carbon atoms, aryl yorsugswelse Phenyl, AralkylVle Bensyl or Phenyläthyl or cycloalkyl such as cyclohexyl; the above substituents in particular the phenyl groups can be substituted as desired;

Z * a simple chemical bond or -HH-; H · - a y-valent organic grouping of those given for U

Kind;
Bj ■ U ₂ * 4 - 8;

■ * 0 or 1; 0 only in the case of n ₂ »0 and n ^ * 4 - 8; y »1,2 or 3.

Ea is these copolymers (in the case α * 1) real block polymers and not compounds, the ethylene oxide and Fropylenojrld in statistical Distribution included.

01 · Connections created in the inventive manner are generally high-quality syrupes. For a photographic application they are used in el-

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Hem photograph! 3cheα inactive solvent, preferably lower aliphatic alcohols, and this dissolving ▼ emulsified into the protective layer before casting. The antistatic agents are then essentially after potting heterogeneously distributed in the form of fine particles in the layer.

The compounds according to the invention are used in amounts of 0.03-0.20 g per g of layered colloid, preferably 0.05-0.75 g per g of layered colloid in layers of a water-permeable colloid such as polyvinyl alcohol, carboxymethyl cellulose or gelatin used. They can be used alone or in combination with surfactants such as anionic or non-ionic wetting agents, or mixed with anti-Newton additives such as 1 - 3 / U large Particles of polystyrene, polymethacrylic acid ester! or Urea-formaldehyde polymers are used. This gives smooth layers with an excellent antistatic effect. "

The compounds to be used in the catfish according to the invention can be used for black and white and color films in emulsion layers, atrial protective layers and NC layers. SI · do not produce a fog, are used as a development accelerator ineffective, do not emerge from the layer and do not lead to gluing.

The antistatic agents are sparingly soluble in water and

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photographlach Inactive. In the case of m = ο you have (cf. general formula) a maximum of 8 ethylene oxide units; at • Compounds with strongly hydrophobic radicals R are preferably compounds with more than 8 Äthylenoxld-Einhelten used so that these compounds are emulsifiable, but in these cases (m = 1 in the general formula) the ethylene oxide chain is interrupted by propylene oxide after about the 7th to 8th ethylene oxide unit. The resulting Compounds also show no development-accelerating effect.

Suitable compounds are, for example, the following substances of the following formulas:

I. C ₁ 3H ₅₇ O- (CH ₂ -CH ₂ 0 ^ ₈ CH ₂ -CH-O ^ CH ₂ -CH ₂ -

CH ₃

II. C ₁₈ H ₅₇ O- (CH ₂ -TCH ₂ O) ₈ CH ₂ -CH-OfCH ₂ -CH ₂ -O) ₈ CONH-C ₆ H ₄ -NO ₂

CH ₃

III. C ₁ QH ₃₇ O- (CH ₂ -CH ₂ O) ₈ CH ₂ -CH -OfCH ₂ -CH ₂ -O) ₈ CO

CH ₃

C ₁₈ H ₃₇ O- (CH ₂ -CH ₂ O) ₈ CH ₂ -CH-Of CH ₂ -CH ₂ -O) ₈ CONH '

CH ₃

17. C ₁₈ H ₃₇ O- (CH ₂ -CH ₂ O) ₈ CH ₂ -CH -OfCH ₂ -CH ₂ -O) ₈ C

CH ₃

C ₁₈ H ₃₇ O- (CH ₂ -CH ₂ O) ₈ CH ₂ -CH-OfCH ₂ -CH ₂ -O) ₈ CC 179 CH ₃ 909833/1142 ^

BATH ORIGINAL

V. C-

CH ₃

VI. C ₁₆ Η _{α 3} Ό- (CH ₂ -CH ₂ O ^ ₈ CH ₂ -CH-OfCH ₂ -CH ₂ -O ^ ₈ CONH-C ₆ H ₄ -NO ₂

OH ₅

▼ II. C ₁₂ H ₂₅ - /% - 0- (CH ₂ -CH ₂ O ^ CH ₂ -CH-OfCH ₂ -CH ₂ -O- \ = s / I

VIII. IsO-C ₉ H ₁₅ - / \ -0-

-CH-OfCH ₂ -CH ₂ -0-) ₇ ^ JOCH,

, -CH-OfCH ₂ -CH ₂ -OJ ₇ CH *

H. C ₁₄ H ₂₉ O- (CH ₂ -

-NO

⁴ V

r ^

CH ₅

XIX

A-G 179

te,

COMH
I.

I.
COMH ...

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1522A08

The compounds to be used in the manner according to the invention are prepared by known methods. For compounds 1 and 7, the preparation is described in detail as follows. The remaining connections will made in the same way.

AG 179 - 7a -

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BATH ORIGINAL

Connection I,

1st stage: V.

270 g of octadecanol and 5 g of potassium hydroxide are dehydrated at 12O ⁰ C and 15 Torr and then reacted with 352 g of ethylene oxide (8 mol) ^{at temperatures between 160 and 170 0 C.} Immediately after this reaction, 58 g of propylene oxide (1 mol) are condensed, then again 352 g of ethylene oxide. For cleaning, the reaction mixture is dissolved in 1.5 l of benzene, refluxed with activated charcoal for 20 minutes and, after suctioning off the charcoal, neutralized with hydrochloric acid. The solvents are removed on a rotary evaporator. The oily, yellow-brown product is filtered at 80 to 90 ⁰ C again.

2nd stage:

52, Og oxalkyllertes octadecanol (as above sbeschrleben) In 150 ml of absolute toluene and stirred after mixing with a solution of 6.0 g Phenyllsocyanat In 100 ml of absolute toluene 'for 5 hours at 110 ⁰ C. The reaction mixture is then boiled for 5 minutes with 1 ml of methanol. After brief boiling with activated charcoal, vacuuming the well and removing the solvent, a light brown product with a honey-like consistency is obtained.

Compound VII.

A mixture of 42 g, analogous to the first stage of compound I, of oxyalkylated n-dodecylphenol, 20 ml of benzene and 5 g of pyridine is used in a solution of 9.9 g of 3 _{t of} 5-dinetrobenzoyl

9 0 9 8 3 3/1 U 2
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BATH ORIGINAL

chlorld Ια 150 ml of benzene is added dropwise for 5 hours at room temperature and 1 hour bet 50 ⁰ C stirred. After cooling, the reaction mixture is poured onto ice, _{acidified with Zn-H 2} , mixed with saturated sodium chloride solution and extracted several times with methylene chloride. After drying, the combined extracts are freed from solvent over KpCO, in vacuo.

Example 1;

A still damp bromiodosilver gelatin emulsion layer, which is on a cellulose acetate base, is covered with a protective layer of about 1.1 - 1.3 / U Thickness. The casting solution for this protective layer has the following composition:

1 kg of gelatin

50 1 water

3.75 1 2 strength aqueous mucochloric acid as hardening agent

0.5 1 7.5 5 * long saponln

0 9 1 10 £ lge methanolic solution of an antistatic

01 · 10 jfige methanolic solution dee Antistatikume is eineoulgiert at temperatures from 30 to 40 ⁰ C under stirring la dta other Glessansatz. The pH of the Schutzscbicbt-Gleeslöaung is adjusted to 6.5 with sodium hydroxide solution.

The protective layer is applied after the emulsion layer has solidified in the rinsing process or at the same time as the application of the emulsion layer according to the vacuum airbruah process. 179 -9- 909833 / 1U2

BATH ORIGINAL

The drying lies behind. fthltrfrei.ee Pllmmattr das ktlat clouds, Strtlftn, Blattu, real btattzbart Stitlltn, outdoor exercise or all-round feeler wholesome and good Plaalagt btaltst.

The test for antlttatltcttt efficacy follows swtltäglgtr IllmatißleruQg dtr Probeetrelfea with the rotlt rtndtu tltktroetatlBOhen power supply unit type PM 300 HR I after Prof. Or. Ing.P. Sohwtuekhagta (Hereteller: Btrglachtr Ptlagträttbau, Wuppertal). Ototttta became dlt Charging height at 60 * RP.

I. V / cm (60 % RP) Type II 150 link III 1 link IV 1 link V 1 link VI 1 link VII. 2 link VIII 2 link IX 0 Blindness X 0 Blindness 2 Blindness 1

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Example 2; H

In a gelatin solution containing antihalation dyes, consisting of

1000 ml of water

110 g gelatin

60 ml 10 X-ig. Vixen

18 ml 5 ig. Chrome alum

4 ml 5 #. Saponin and

30 ml of alcohol

15 ml of a 10 ^ strength methanolic solution are one of the above-mentioned antistatic agents, as described in Example 1, “inetaulgisrt. This casting solution is on a transparent Cellulose acetate film base potted and dried. On the non-layered side of the cellulose acetate pad can be a silver halide emulsion layer in the usual manner be applied; the back of the layer described in more detail above then serves as the NC layer.

Antistatic testing of the casting samples as in example 1:

V / cm (60 1o RF)

Loading III Compound IV Loading VI

1200 150 HO

180

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Example 3: ¥ i

Ια a gelatin solution consisting of

1000 ml of water

30 g gelatin

7 »5 al 5 £ lg 'TriacryIformal

15 oil 5 #lg. Saponln

15 ml of a 10 solution of one of the antistats mentioned Uta, as described in Example 1, elnetnulglert. These Solution is applied as a protective layer to the emulsion layers of a multilayered color photographic material and dried.

Antistatic testing of the casting samples as in example 1:

III V / cm (60 + RP) Type IV 100 link VI 15th link 24 link 12th

Example 4t

It is a photographic material with a silver bromide iodine emulsion layer and an uppermost protective layer containing no antistatic agent is treated with:

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0.01-0.25 # solutions of the following Antistatic agents

a) in water or

b) in methylene chloride.

The charge level of the conditioned samples at 60 $ RF is being measured. The comparative measurements relate to samples of the same photographic material, but treated only with water or methylene chloride.

Antistatic testing of the casting samples:

a) Application of the antistatic from aqueous solution:

V / cm (60 % RH)

without antistatic compound V
Connection X

120 50 12

b) Application of the antistatic from methylene chloride solution:

V / cm (60 * RP)

without antistatic compound V
Connection X

20 0.5 2

Example 5:

In the following example, the possibility of combinations of the antistatic agents according to the invention with known

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will show. Babel become representatives of two groups of antistatic Medium used, namely

a) Polystyrene sulfonic acid as a representative of high molecular weight compounds that contain carboxyl or sulfonic groups and

^) various alkali salts (with the exception of NaCl), do not flake the gelatin.

The antistatic agents are incorporated into a protective gelatin layer which is applied to a silver bromide iodine coating according to Example 1. Based on the gelatin · trockengewlcht layer contains alone or in combination - as can be seen from the following tables - 20 i "of the antistatic agent erflnduagsgemässen wt i> polystyrene sulfonic acid (PSS), 6 wt 1» Alkallsalz or 6 wt....

After the application of the protective layer, the photographic Material dried and after 2 days of air conditioning (60 # Room humidity) checked the antistatic properties. The results can be seen from the following table:

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• + PSS Legal statements Charging
la
Volts / cm Surface
resisted
la 10IO ohms ♦ + Alkali salt 150 8.1 - ___ Qelatlneechicht without antistatic
additions - Layers with ί + + KNO-
J
+ Na ₂ SO ^ 15th 2.1 Cargo load
oäeaee anti
etatikum + 0.5 0.9 ...... + KNO,
+ Na ₂ SO ^ 0.5
0.5 0.7
0.9 Terbladg III - 9 1.5 R.
N - + KNO ₃ 3
4th 1.2
1.2 Il + Na ₂ SO ₄ 3 1.6 W.
m +
• 1 1.4 Yerbladg IV + KNO ₃ 1 1.4 W. ... + Na ₂ SO ₄ 1.5 1.3 H IM 11 M 1 0.9 n ♦ KNO, 1 1.2 It ♦ Na ₂ SO ₄ 0.2 2.2 1" + 0.5 1.5 t
Terbladg TI + KNO ₃ 0.4 1.1 IT + Na ₂ SO ₄ 1 2 1" 2.5 1.5 It 1 * It

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The level of charge was as described in Example 1 Method · measured. The surface forest status is baatlmmt with tinem Maaagarät the PIrma linden leaf, Electrical engineering and electronics »Berlln-Halensee. Daa device has swal in a distance of 2 cm parallel running, 10 cm long comb electrodes against which the adequately air-conditioned samples are pressed with constant pressure will. The resistances are read on a connected ohmmeter.

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Claims (1)

- ■ 1527408 Patent claims: (1.JPhotograph! Βchee material with an antistatic Layer, characterized in that the antistatic layer is a compound which is sparingly soluble in water contains the following formula: / RO- (CH ₂ -CH ₂ -O) _n - (CH ₂ -CH-O) _n - (CH ₂ -CH ₂ -O) _n -CO Xj ^ CH, where mean: H _ alkyl with 6-18 carbon atoms, aryl, aralkyl or Cycloalkyl;
X a is an organic chemical bond or -NH-j R * »a y-valent group of the type indicated for R; nj »n ₂ a 4 - 8 ο β 0 or 1; O only in the case of n ₂ = 0 and a ^ = 4-8 y «1, 2 or 3 2. Photographic material according to claim 1, characterized in that that the compound is present in amounts of 0.03-0.20 g per g layer binder let. 5. Photograph! Βeheε material according to claim i _t, characterized in that the antistatic Hittal is contained in a heterogeneous distribution in its layer. AG 179 - 17 - 909833 / 1U2